Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Page 6 of 8
ARTICLE
Journal Name
136.7 (d, 1JCF = 249 Hz, m-C
1
2
1
1
38.3 (d, 1JCF = 248 Hz, p-C
33 Hz, m-C
), 132.5 (Ar), 132.1 (Ar), 130.2 (Ar), 130.0 (Ar), 129.5 (Ar), 129.3 (Ar), 128.4 (Ar), 128.0 (pyD)O, 1I:2106..1703(m9/C-p9yD)T,01427631.0J
29.9 (Ar), 129.7 (Ar), 129.6 (Ar), 129.5 (Ar), 129.2 (Ar), (Ar), (m-Arring), 125.8 (HCCH ), 123.2 (HCNCH ), 121.9 (HCNCH ), 52.4
29.1 (Ar), 129.0 (Ar), 128.9 (Ar), 128.5 (Ar), 128.4 (Ar), 128.3 (CH Ph), 51.8 (Cring ). Some ipso carbons are not observed.; B
Cl , 128 MHz): δ -9.0 (d, JBH = 100 Hz, BH ), -16.6 (s,
6
F
5
), 137.0 (p-Arring), 136.3 (d, 1JCF
=
6 5
F
2
2
2
1
1
2
H
2
1
+
(Ar), 127.9 (Ar), 127.7 (Ar), 126.9 (Ar), 126.4 (Ar), 126.4 (Ar), NMR (CD
2
2
1
9
1
26.0 (Ar), 125.6 (Ar), 125.5 (Ar), 8a: δ 139.3 (BCCH), 137.8 B(C
MeCCH), 54.0 (Cring ), 52.1 (CH
BCCH), 139.6 (MeCH), 52.1 (Cring ), 54.1 (CH
, 128 MHz): δ 55.4 (s, Synthesis
, 376 MHz): δ -132.7 [C (NCH(BC(CHNCH
), -166.6 (t, A solution of 3 (206 mg, 0.20 mmol) in 1 mL C
to a mixture of tBu P (41 mg, 0.20 mmol) with B(C
.10 mmol) in 2 mL toluene. The combined solution was left at
room temperature for 16 h. Insoluble yellow crystals, combined
(10) These compounds were with colorless crystals of [tBu PH][B(C ], were formed from
prepared in a similar fashion and thus only one preparation is the solution. The solvent was decanted. The crystals were
detailed. Ethyldiphenylphosphane (11.4 mg, 0.054 mmol, 1.02 washed with cold C Br (3 × 0.5 mL) and pentane (3 × 0.5 mL),
equiv.) was added to 1 mL CHCl . The clear colourless solution and were dried in vacuo. 11 was collected in 47% yield. Single
6 5
F
)
4
); F NMR (CD
2
Cl
2
, 376 MHz): δ -132.6 (m, br, o-C
6
F
).
5
), -
3
3
(
(
H
2
2
), 17.8 (Me), 8b: δ 140.3 162.9 (t, JFF = 21 Hz, p-C
6
5
F ), -166.7 (t, JFF = 19 Hz, m-C
F
6 5
H
2
2
), 16.5 (Me). Ipso
1
1
carbons are not observed.; B NMR (CDCl
3
of
+
19
br, B ), -16.7 (s, B(C
6
F
5
)
4
); F NMR (CDCl
3
2
H
2
2
C
6
H
4
)
2 6
)C H
4
)(NCH(B(C
6
F
H
6 5
5
)
3
)C
Br was added
(51 mg,
6 4
H )CB] 12
3
3
(
d, JFF = 14 Hz, o-C
J
6
F
).
5
), -162.5 (t, JFF = 21 Hz, p-C
F
6 5
3
FF = 19 Hz, m-C
6
F
5
3
6 5 3
F )
0
Synthesis of [PhCH
Ph PCCH (9), L = NC
2
(CHN)
C(H)CH
2 2
CCH C
6
H
4 6 5 4
B(H)L][B(C F ) ]
L
=
2
5
H
4
2
3
6 5 4
F )
6 5
H
3
formed was added to 2 (50mg, 0.053 mmol, 1 equiv.). The crystals for X-ray studies were obtained by layering a saturated
1
solution was dried to a white sludge. The solid was washed with solution in o-C
6
H
4
Cl
2
with pentane to give yellow crystals. H
3
pentane and dried to a white powder. (9): Yield: 55 mg, 90 %; NMR (600 MHz, CDCl
3
,): δ 8.35 (d, JHH = 8 Hz, 2H, PhH), 8.29
, 400 MHz): δ 7.70 – 7.61 (m, 5H, Ar), 7.58 – 7.53 (dd, JHH = 8 Hz, JHH = 2 Hz, 2H, PhH), 7.94 (d, JHH = 2 Hz, 2H, -
m, 2H, Ar), 7.48 – 7.43 (m, 2H, Ar), 7.41 – 7.36 (m, 3H, Ar), 7.31 NCH-), 7.87 (d, JHH = 8 Hz, 2H, PhH), 7.77 (td, JHH = 8 Hz, JHH
7.24 (m, 3H, Ar), 7.19 – 7.15 (m, 2H, Ar), 7.14 (s, 1H, HCNC), 1 Hz, 2H, PhH), 7.66 (t, JHH = 8 Hz, 2H, PhH), 7.54 – 7.48 (m, 5H,
1
3
4
4
H NMR (CDCl
3
3
3
4
(
=
3
–
7
2
2
.04 – 7.02 (m, 2H, Ar), 6.96 (s, 1H, HCNC), 5.33 (d, JHH = 15 Hz, PhH & -CH-), 7.40 (m, 5H, PhH & -CH-) 5.58 – 5.47 (m, 4H, -CH -
2
5
13
1
1
H, CH
2
), 4.98 (dd, JHH = 16 Hz, JHP = 4 Hz, 1H, Cring
H
2
), 4.66 (d, ); C{ H} NMR (126 MHz, CDCl
3
): δ 141.3, 136.7, 135.8, 134.4,
), 3.96 (s, 133.5, 131.7, 130.2, 129.2, 128.8, 128.4, 127.1, 127.0, 126.4,
2
2
J
HH = 15 Hz, 1H, CH
2
), 4.64 (d, JHH = 16 Hz, 1H, Cring
H
2
br, 1H, BH ), 3.47 (d, JHP = 9 Hz, 1H, HCC); 13C{ H} NMR (CDCl
+
3
1
125.5, 122.7, 121.1, 50.8; B NMR (128 MHz, CDCl
11
,): δ -9.6 (s),
] anion is omitted):
), -133.1 (d, JFF = 24 Hz,
3
,
3
1
), 138.3 (dt, 1JCF = 244 -14.6 (s); F NMR (377 MHz, CDCl
), 136.4 (d, JCF = 249 Hz, m-C
19
-
1
25 MHz): δ 148.4 (d, JCF = 241 Hz, o-C
6
F
5
, [B(C F )
3 6 5 4
3
1
3
3
Hz, JCF = 17 Hz, p-C
6
F
5
6
F
5
), 136.3 δ -132.9 (dd, JFF = 52, 24Hz, 1F, o-C
F
6 5
3
3
5
3
(d, JCP = 5 Hz, BCCCH), 136.0 (d, JCP = 6 Hz, BCCH), 133.9 (d, JCP 1F, o-C
F
6 5
), -133.9 (dd, JFF = 46, 24Hz, 1F, o-C
F
6 5
), -135.0 (m, 1F,
), -141.3 (d, JFF
4
3
3
=
C
o-C
P-o-C
=
C
3 Hz, BCCCHCH), 133.9 (d, JCP = 3 Hz, BCCHCH), 133.1 (B-ipso- o-C
6
F
5
), -136.6 (dd, JFF = 52, 24Hz, 1F, o-C
F
6 5
=
2
2
), -167.5 (t, 3JFF = 21 Hz, 1F, p-C
H
6 4
), 132.3 (d, JCP = 11 Hz, P-o-C
), 130.3 (d, JCP = 12 Hz, P-o-C
6
H
5
), 132.2 (d, JCP = 11 Hz, P- 24 Hz, 1F, o-C
6
F
5
F
6 5
), -168.0 (t,
), -168.4 (t, 3JFF = 21 Hz, 1F, p-C
), -171.1
), -171.6 (t, 3JFF = 21 Hz, 1F, m-C
), -
), -172.3 (t, 3JFF = 21 Hz, 1F, m-
), -175.0 (t, 3JFF = 21 Hz,
); P{ H} NMR (162 MHz, CDCl ): δ 59.8 (s).
2
2
3
H
6 5
6
H
5
), 129.9 (d, JCP = 11 Hz,
J
FF = 21 Hz, 1F, p-C
3
6
F
5
6 5
F
6
H
5
), 129.6 (CH
2
-p-C
6
H
5
4
), 129.5 (CH
2
-m-C
6
H
5
), 128.2 (d, 3JCP (t, JFF = 24 Hz, 1F, m-C
F
6 5
6 5
F
3
4 Hz, P-m-C
6
H
5
), 128.1 (d, JCP = 4 Hz, P-p-C
6
F
5
), 128.0 (CH
2
-o- 171.7 (t, JFF = 19 Hz, 1F, m-C
F
6 5
4
4
3
H
6 5
), 126.1 (d, JCP = 4 Hz, HCNCBP), 122.4 (d, JCP = 38 Hz,
6 5 6 5
C F ), -173.2 (t, JFF = 21 Hz, 1F, m-C F
1
1
31
1
HCNCBP), 122.3 (d, JCP = 65 Hz, P-ipso-C
Hz, P-ipso-C
Hz, HCCP), 52.9 (CH
carbons are not observed.; P{ H} NMR (CDCl
6
F
5
), 120.3 (d, JCP = 68 1F, m-C
), 102.3 (d, 2JCP = 9 Hz, HCCP), 70.4 (d, JCP = 109
F
6 5
3
1
6
F
5
4
2
), 52.4 (d, JCP = 3 Hz, Cring
H
2
). Some ipso Synthesis of [tBu
, 162 MHz): δ - 3 (206 mg, 0.200 mmol) in 2 mL C
, 128 MHz): δ -16.0 (s, B(C ), -22.0 (s, of tBu P (81 mg, 0.400 mmol) with B(C
, 376 MHz): δ -132.5 (d, JFF = 10 Hz, o- mmol) in 2 mL C Br. The combined solution was left at room
3
PH][C
2
H
2 6 5
(NCH(B(C F )
3
)
2
CB] 13. A solution of
Br was added to a mixture
(205 mg, 0.400
3
1
1
3
6 5
H
1
1
8
.31 (s); B NMR (CDCl
3
6
3
F
5
)
4
3
6 5 3
F )
+
19
br, BH ); F NMR (CDCl
C
C
3
6 5
H
3
6
F
F
5
), -162.8 (t, 3JFF = 21 Hz, p-C
).
6
F
5
), -166.6 (t, JFF = 20 Hz, m- temperature for 16 h. The resulting green solution was mixed
6
5
with 4 mL of pentane and left at room temperature for 24 h.
(
10): White powder. Crystals suitable for X-ray crystallography Insoluble yellow needle crystals formed from the solution. The
were obtained by slow evaporation of a chloroform solution. solvent was decanted. Crystals were washed with C
6
H
5
Br (3 ×
0.5 mL) and pentane (3 × 0.5 mL), and were dried in vacuo,
PH][B(C ]. While these
1
3
Yield: 41 mg, 98 %; H NMR (CD
2
Cl
2
, 400 MHz): δ 8.56 (d, JHH
=
3
3
6
Hz, 1H, BCCH), 8.00 (t, JHH = 8 Hz, 1H, p-Arring), 7.53 (t, JHH = 8 affording a mixture of 13 and [tBu
3
6 5 4
F )
3
Hz, 2H, m-Arring), 7.39 (d, JHH = 2 Hz, 1H, HCNCH
py), 7.31 (d, JHH = 3 Hz, 1H, HCNCH
7
2
), 7.36 (m, 2H, species were not separable in bulk, NMR data revealed a yield
3
1
3
2
3
), 7.27 – 7.20 (m, 5H, Ar), of 13 of 77%. H NMR (600 MHz, CDCl
3
, 298K): δ 7.86 (d, JHH
=
3
3
4
.09 (d, JHH = 8 Hz, 1H, o-py), 6.77 (d, JHH = 7 Hz, 1H, m-py), 6.70 8 Hz, 2H, PhH), 7.72 (d, JHH = 8 Hz, 2H, PhH), 7.51 (d, JHH = 2 Hz,
3
3
3
3
3
(dd, JtransHH = 18 Hz, JcisHH = 11 Hz, 1H, HCCH
2
), 5.64 (d, JcisHH
=
1H, -NCH-), 7.39 (d, JHH = 8 Hz, 2H, PhH), 7.33 (d, JHH = 8 Hz, 2H,
Ph), 5.54 (d, 2JtransHH = 25 Hz, Ph-H), 7.11 (d, JHH = 9 Hz, 2H, -N-CH-B(C
3
F )
5 3
-); 13C{ H} NMR
1
1
1
7 Hz, 1H, HCCH
2
), 5.59 (s, 2H, CH
), 5.04 – 4.85 (m, 2H, Cring
2
6
+
H, HCCH
2
H
2
), 4.59 – 4.00 (s, br, BH ); (126 MHz, CDCl
3
): δ 151.7, 149.3, 147.4, 137.4, 134.6, 131.9,
131.7, 130.2, 127.0, 125.7, 122.7, 37.7 (PC), 30.1 (-CH
1
3
1
1
11
C{ H} NMR (CD
2
Cl
2
, 125 MHz): δ 149.2 (BCCH), 148.6 (d, JCF
=
3
);
B
);
1
2
43 Hz, o-C
6 5
F ), 143.7 (p-Arring), 138.6 (d, JCF = 239 Hz, p-C
6 5
F
), NMR (128 MHz, C Br, B(C ] omitted): δ -9.8 (s, -B(C
6
D
5
6
F
5
)
4
6
F
)
5 3
6
| J. Name., 2019, 00, 1-3
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